TY - JOUR
T1 - Structural Elucidation of the Mechanism of Molecular Recognition in Chiral Crystalline Sponges
AU - Zhang, Shi Yuan
AU - Fairen-Jimenez, David
AU - Zaworotko, Michael J.
N1 - Publisher Copyright:
© 2020 The Authors. Published by Wiley-VCH GmbH
PY - 2020/9/28
Y1 - 2020/9/28
N2 - To gain insight into chiral recognition in porous materials we have prepared a family of fourth generation chiral metal–organic frameworks (MOFs) that have rigid frameworks and adaptable (flexible) pores. The previously reported parent material, [Co2(S-mandelate)2(4,4′-bipyridine)3](NO3)2, CMOM-1S, is a modular MOF; five new variants in which counterions (BF4−, CMOM-2S) or mandelate ligands are substituted (2-Cl, CMOM-11R; 3-Cl, CMOM-21R; 4-Cl, CMOM-31R; 4-CH3, CMOM-41R) and the existing CF3SO3− variant CMOM-3S are studied herein. Fine-tuning of pore size, shape, and chemistry afforded a series of distinct host–guest binding sites with variable chiral separation properties with respect to three structural isomers of phenylpropanol. Structural analysis of the resulting crystalline sponge phases revealed that host–guest interactions, guest–guest interactions, and pore adaptability collectively determine chiral discrimination.
AB - To gain insight into chiral recognition in porous materials we have prepared a family of fourth generation chiral metal–organic frameworks (MOFs) that have rigid frameworks and adaptable (flexible) pores. The previously reported parent material, [Co2(S-mandelate)2(4,4′-bipyridine)3](NO3)2, CMOM-1S, is a modular MOF; five new variants in which counterions (BF4−, CMOM-2S) or mandelate ligands are substituted (2-Cl, CMOM-11R; 3-Cl, CMOM-21R; 4-Cl, CMOM-31R; 4-CH3, CMOM-41R) and the existing CF3SO3− variant CMOM-3S are studied herein. Fine-tuning of pore size, shape, and chemistry afforded a series of distinct host–guest binding sites with variable chiral separation properties with respect to three structural isomers of phenylpropanol. Structural analysis of the resulting crystalline sponge phases revealed that host–guest interactions, guest–guest interactions, and pore adaptability collectively determine chiral discrimination.
KW - chiral binding sites
KW - chiral crystalline sponge
KW - chiral metal–organic frameworks
KW - chiral separation and resolution
KW - molecular recognition
UR - http://www.scopus.com/inward/record.url?scp=85089197033&partnerID=8YFLogxK
U2 - 10.1002/anie.202006438
DO - 10.1002/anie.202006438
M3 - Article
C2 - 32589318
AN - SCOPUS:85089197033
SN - 1433-7851
VL - 59
SP - 17600
EP - 17606
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 40
ER -